EP3068932A1 - Fibres luminescentes, articles comprenant lesdites fibres, et procédés de formation desdites fibres - Google Patents

Fibres luminescentes, articles comprenant lesdites fibres, et procédés de formation desdites fibres

Info

Publication number
EP3068932A1
EP3068932A1 EP14862807.6A EP14862807A EP3068932A1 EP 3068932 A1 EP3068932 A1 EP 3068932A1 EP 14862807 A EP14862807 A EP 14862807A EP 3068932 A1 EP3068932 A1 EP 3068932A1
Authority
EP
European Patent Office
Prior art keywords
luminescent
fibers
polycyclic compound
fiber
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14862807.6A
Other languages
German (de)
English (en)
Other versions
EP3068932A4 (fr
EP3068932B1 (fr
Inventor
Thomas Potrawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honeywell International Inc filed Critical Honeywell International Inc
Publication of EP3068932A1 publication Critical patent/EP3068932A1/fr
Publication of EP3068932A4 publication Critical patent/EP3068932A4/fr
Application granted granted Critical
Publication of EP3068932B1 publication Critical patent/EP3068932B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/16—Addition of dyes to the spinning solution
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D21H13/08—Synthetic cellulose fibres from regenerated cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • the technical field generally relates to luminescent fibers that include a luminescent compound, articles including the luminescent fibers, and methods of forming the luminescent fibers. More particularly, the technical field relates to luminescent fibers that include an organic luminescent compound that retains luminescent properties after forming the luminescent fibers, articles including the luminescent fibers, and methods of forming the luminescent fibers.
  • Luminescent fibers are known for use in various authentication applications.
  • value documents such as banknotes and checks often include the luminescent fibers to provide one mechanism for authentication of the value documents.
  • the luminescent fibers are generally incorporated in or on the value documents, often within substrate material of the value documents such as paper stock, and the luminescent fibers are generally difficult to remove or add to the substrate material after original production of the value documents.
  • Conventional luminescent fibers are dyed with organic luminescent dyes that emit radiation upon stimulation by UV or visible light, with the emitted radiation detected either by human or machine observation.
  • Regenerated cellulose such as, but not limited to, cupro, lyocell, viscose, and modal, are commonly employed as the luminescent fibers due to excellent compatibility with paper stock.
  • incorporation of conventional organic luminescent dyes into the fibers that include the regenerated cellulose while retaining luminescent properties of the luminescent dyes is often challenging.
  • regeneration processes that are employed to form the regenerated cellulose often involve harsh processing conditions and employ compounds that denature the organic luminescent dyes.
  • luminescent dyes are coated on surfaces of the fibers that include the regenerated cellulose after production of the fibers.
  • surface coatings are subject to wear and may exhibit breakdown or change of the luminescent properties due to environmental conditions such as humidity and pH.
  • inorganic pigments in particulate form have been incorporated into the fibers that include the regenerated cellulose, the inorganic pigments generally exhibit high abrasivity and generally must be present in high densities, both of which features modify the basic physical properties of the fibers that include the regenerated cellulose. Further, high loading of the inorganic pigments is generally required to achieve sufficiently high luminescent emissions.
  • luminescent fibers that include organic luminescent compounds that retain luminescent properties even when present under harsh conditions associated with regenerating cellulose such that the organic luminescent compounds can be incorporated within the fibers that include the regenerated cellulose, as opposed to only coating a surface of the fibers that include the regenerated cellulose.
  • articles including the luminescent fibers and methods of forming the luminescent fibers are desirable.
  • a luminescent fiber includes a regenerated cellulose and a luminescent polycyclic compound.
  • the luminescent polycyclic compound includes a heterocyclic ring.
  • the heterocyclic ring includes two nitrogen atoms therein.
  • an article in another embodiment, includes a substrate and luminescent fibers incorporated in the substrate.
  • the luminescent fibers include a regenerated cellulose and a luminescent polycyclic compound.
  • the luminescent polycyclic compound includes a heterocyclic ring.
  • the heterocyclic ring includes two nitrogen atoms therein.
  • a method of forming luminescent fibers includes combining a cellulose solution and a luminescent polycyclic compound to produce a fiber- forming composition.
  • the luminescent polycyclic compound includes a heterocyclic ring.
  • the heterocyclic ring includes two nitrogen atoms therein.
  • the fiber-fonning composition is spun to form the luminescent fibers.
  • FIG. 1 is a perspective view of an exemplary embodiment of an article including a substrate and luminescent fibers incorporated in the substrate;
  • Luminescent fibers articles including the luminescent fibers, and methods of forming the luminescent fibers are provided herein.
  • the luminescent fibers include a regenerated cellulose and a luminescent polycyclic compound.
  • regenerated cellulose refers to cellulose that is chemically modified through various conventional processes for conversion into semi-synthetic polymer fibers that are generally known as rayon.
  • luminescent polycyclic compound is a compound that has at least two identifiable cyclic groups that may or may not share common bonds within the ring structures.
  • the luminescent polycyclic compound includes a heterocyclic ring that has two nitrogen atoms in the heterocyclic ring, i.e., the heterocyclic ring includes at least two nitrogen atoms as part of the ring structure in the heterocyclic ring.
  • the luminescent polycyclic compound retains luminescent properties even when present under harsh conditions associated with regenerating cellulose. Without being bound to any particular theory, it is believed that the heterocyclic ring that includes the two nitrogen atoms provides excellent stability to the luminescent polycyclic compound and enables the luminescent polycyclic compound to retain luminescent properties even when exposed to harsh conditions, such as alkaline conditions, that are associated with regenerating cellulose.
  • the luminescent polycyclic compound may be combined in a cellulose solution during regeneration of the cellulose, prior to spinning, with the luminescent polycyclic compound being present throughout a bulk of the luminescent fibers after spinning, as opposed to only coating a surface of the luminescent fibers.
  • an article 10 that includes a substrate 12 and luminescent fibers 14 incorporated in the substrate 12.
  • incorporated means that the luminescent fibers 14 may be included in or on the substrate 12.
  • the luminescent fibers 14 may be adhered to a surface of the substrate 12, or may be present both on the surface and beneath the surface of the substrate 12.
  • Specific types of articles 10 that can be employed for purposes herein are not particularly limited and, in various embodiments, the substrate 12 may be rigid or flexible and may be formed from one or more layers or components.
  • the "substrate 12,” as referred to herein, is an object into which the luminescent fibers 14 are incorporated, and it is to be appreciated that additional layers or objects may be disposed over the substrate 12 so long as the luminescent fibers 14 can be exposed to light and observed for purposes of authentication.
  • the substrate 12 includes a base material selected from paper, paper pulp, a polymer, plastic, plastic base resin, glass, metal, a textile, fiber, ceramic, wood, a slurry, or a combination thereof.
  • the variety of configurations of substrate 12 are too numerous to mention, as the luminescent fibers 14 described herein may be used in conjunction with a vast array of different types of articles 10. Therefore, although an article 10 that includes a simple, unitary substrate 12 is illustrated in FIG.
  • substrate 12 may have any of a variety of different configurations.
  • suitable articles 10 that can include the luminescent fibers 14 include, but are not limited to, an identification card, a driver's license, a passport, identity papers, a banknote, a check, a document, a paper, a stock certificate, a packaging component, a credit card, a bank card, a label, a seal, or a postage stamp.
  • the substrate 12 may include numerous other features, for security or otherwise, in addition to the luminescent fibers 14 that are described herein.
  • the luminescent fiber includes regenerated cellulose and a luminescent polycyclic compound.
  • Any conventional regenerated cellulose may be suitable for the luminescent fiber, and the regenerated cellulose may include rayon.
  • suitable regenerated cellulose include, but are not limited to, those chosen from the group of cupro, ryocell, viscose, modal, or combinations thereof.
  • the aforementioned examples of regenerated cellulose differ by mode of manufacture and various requirements of the cellulose that is subject to regeneration (e.g., lignin-containing or lignin-free), and the various examples of the regenerated cellulose have different physical properties.
  • the regenerated cellulose is formed by first forming a cellulose solution through conventional techniques.
  • cupro may be formed through the cuprammonium method using an ammoniac copper hydroxide to dissolve the cellulose and form a cellulose solution.
  • lyocell may be formed through the lyocell process using n-methylmorpholine n-oxide to dissolve the cellulose and form a cellulose solution.
  • viscose may be formed by treating cellulose with sodium hydroxide and carbon disulfide to form a cellulose solution.
  • Viscose is particularly suitable for the luminescent fibers 14 when the luminescent fibers 14 are to be included in articles 10 that have the substrate 12 that includes paper, since the luminescent fiber that includes viscose is highly compatible with customary paper stocks based on cellulose and printable by various printing processes, such as offset, so that there are no problems with using such luminescent fibers 14 for marking papers, specifically value documents.
  • the cellulose is regenerated under harsh conditions that destroy luminescent properties of various conventional organic luminescent compounds.
  • the cellulose is generally regenerated under alkaline conditions and at basic pH.
  • the luminescent polycyclic compounds described herein are capable of withstanding the harsh regenerating conditions while retaining luminescent properties, thereby enabling the luminescent polycyclic compound to be combined with the cellulose solution prior to spinning.
  • the luminescent fiber is formed by combining the cellulose solution and the luminescent polycyclic compound to produce a fiber-forming composition, followed by spinning the fiber-forming composition.
  • the luminescent polycyclic compound may be combined with the cellulose at any time prior to spinning the fiber- forming composition to form the luminescent fibers 14.
  • the cellulose may be regenerated in the cellulose solution in the presence of the luminescent porycyclic compound to form the fiber-forming composition prior to spinning, i.e., the luminescent polycyclic compound may be present in the cellulose solution at the same time as other compounds that are employed to regenerate the cellulose.
  • the luminescent fibers 14 are cut to a desired size. Dimensions of the resulting luminescent fibers 14 are not particularly limited. However, in embodiments, the luminescent fibers 14 have an average nominal diameter of from about 3.3 to 28 dtex, and may have a length of from about 2 to 6 mm.
  • the luminescent polycyclic compound includes at least two identifiable cyclic groups that may or may not share common bonds within the ring structures. At least one of the cyclic groups is a heterocyclic ring that includes two nitrogen atoms as part of the ring structure. As alluded to above, it is believed that the heterocyclic ring that includes two nitrogen atoms provides excellent stability to the luminescent polycyclic compound and enables the luminescent polycyclic compound to retain luminescent properties even when exposed to harsh conditions, such as alkaline conditions, that are associated with regenerating the cellulose.
  • suitable heterocyclic rings that may be included in the luminescent polycyclic compound include unsaturated six-membered nitrogen heterocycles such as, pyrazine, pyrimidine and pyridazine, each of which exhibit excellent stability and have stable aromatic rings. All rings in the luminescent polycyclic compound may be heterocyclic, or the luminescent polycyclic compound may have a combination of carbon rings and heterocyclic rings.
  • the luminescent porycyclic compound is a luminescent bicyclic compound that includes the heterocyclic ring and one additional ring.
  • suitable luminescent bicyclic compounds include, but are not limited to, substituted or unsubstituted quinoline or substituted or unsubsthuted quinazolinone.
  • the luminescent polycyclic compound emits radiation in the visible and/or infrared spectrum.
  • Commercially available luminescent polycyclic compounds that include organic derivatives of quinazolinone are sold under the tradename Lumilux® by Honeywell International, Inc.
  • Lumilux® products are Lumilux® Yellow CD 792 and
  • the luminescent polycyclic compound is present in the luminescent fiber in an amount of at least about 1 weight %, such as from about 1 to about 5 weight %, based on the total weight of the luminescent fiber.
  • the luminescent polycyclic compound retains luminescent properties despite being present during regeneration of the cellulose under harsh conditions. Luminescence may be measured in accordance with a lightfastness test whereby a round cuvette ( ⁇ 5 cm) is filled with luminescent fibers 14. The luminescent fibers 14 are irradiated using conventional sun simulation equipment, such as a Honle SOL 2 unit (sun light behind window class).
  • Fluorescent intensity may be determined under irradiation from a 366 nm UV lamp, with a Luminancemeter from Minolta employed to determine fluorescent intensity in the visible green to yellow spectrum.
  • the luminescent fibers 14 exhibit at least 85% retention of relative intensity in the visible green to yellow spectrum after an irradiation time of 35 hours using the Honle SOL 2 unit
  • the luminescent fibers 14 that include the luminescent polycyclic compounds described herein also exhibit excellent chemical resistance to various agents, such as hydrochloric acid, sulfuric acid, ethanol, acetone, and xylene, as determined by retention of fluorescent intensity after exposure to the aforementioned agents.
  • the luminescent fibers 14 that include the luminescent polycyclic compounds described herein also exhibit excellent thermal stability, as determined by retention of fluorescent intensity after a duration of 30 minutes in an oven at 120°C internal ambient temperature.
  • Fibers are prepared in accordance with the following procedure:
  • a cellulose solution was prepared by treating cellulose with sodium hydroxide and carbon disulfide to form the cellulose solution in accordance with conventional viscose fiber preparation techniques. Prior to spinning the cellulose solution into fibers, the following luminescent compounds shown in TABLE I were added to the cellulose solution in an amount of 3 weight %, based on the total weight of the cellulose solution.
  • Lumilux ® Yellow CD 792, Lumilux ® Yellowgreen CD 394, and Lumilux ® Green CD 308 are all quinazolinone class luminescent polycyclic compounds.
  • the cellulose solution is spun to form luminescent fibers 14.
  • the luminescent fibers 14 of Example C also failed to exhibit luminescent properties, although it is believed that the failure of Example C to exhibit luminescent properties is due to excessive solubility of the luminescent compound under the harsh alkaline and acid conditions of the cellulose spinning procedure, and is not associated with destruction of the luminescent compound.
  • the luminescent compound of Comparative Example A was not combined into the cellulose solution.
  • Luminescent compounds in the benzoxazinone class have exhibited no fluorescent effect after including in cellulose solutions due to destruction of the benzoxazinone class luminescent compounds under the harsh conditions within the cellulose solutions during viscose preparation. It is believed that benzoxazinone class compounds are destroyed because the heterocyclic ring only includes a single nitrogen atom.
  • the viscose fibers of Comparative Example A were prepared by first spinning the viscose fibers and then reactive dyeing the viscose fibers with the benzothiazole class reactive dye.
  • Example A exhibited about a +1% retention of fluorescent intensity after an irradiation time of 35 hours using the Honle SOL 2 unit, indicating that Example A not only retained its original fluorescent intensity, but actually exhibited increased fluorescent intensity after irradiation for 35 hours. Although this result was not investigated in detail, it is assumed that under irradiation the bleaching of the viscose is faster than the deterioration of the fluorescent compound. The whiter the viscose, the more intense the fluorescence.
  • Example B exhibited about a -12% retention of fluorescent intensity after an irradiation time of 35 hours using the Honle SOL 2 unit Comparative Example A exhibited a substantial retention of fluorescent intensity after an irradiation time of 35 hours using the Honle SOL 2 unit.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne des fibres luminescentes, des articles qui comprennent lesdites fibres luminescentes, et des procédés de formation desdites fibres luminescentes. Dans un mode de réalisation, une fibre luminescente comprend une cellulose régénérée et un composé polycyclique luminescent. Le composé polycyclique luminescent comprend un anneau hétérocyclique. L'anneau hétérocyclique comprend deux atomes d'azote.
EP14862807.6A 2013-11-14 2014-11-04 Fibres luminescentes, articles comprenant lesdites fibres, et procédés de formation desdites fibres Not-in-force EP3068932B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201361904216P 2013-11-14 2013-11-14
US14/524,221 US20150132575A1 (en) 2013-11-14 2014-10-27 Luminescent fibers, articles including the same, and methods of forming the same
PCT/US2014/063779 WO2015073250A1 (fr) 2013-11-14 2014-11-04 Fibres luminescentes, articles comprenant lesdites fibres, et procédés de formation desdites fibres

Publications (3)

Publication Number Publication Date
EP3068932A1 true EP3068932A1 (fr) 2016-09-21
EP3068932A4 EP3068932A4 (fr) 2017-03-29
EP3068932B1 EP3068932B1 (fr) 2019-04-17

Family

ID=53044049

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14862807.6A Not-in-force EP3068932B1 (fr) 2013-11-14 2014-11-04 Fibres luminescentes, articles comprenant lesdites fibres, et procédés de formation desdites fibres

Country Status (5)

Country Link
US (1) US20150132575A1 (fr)
EP (1) EP3068932B1 (fr)
CN (1) CN105874109B (fr)
ES (1) ES2729070T3 (fr)
WO (1) WO2015073250A1 (fr)

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Also Published As

Publication number Publication date
WO2015073250A1 (fr) 2015-05-21
US20150132575A1 (en) 2015-05-14
CN105874109B (zh) 2019-01-01
EP3068932A4 (fr) 2017-03-29
EP3068932B1 (fr) 2019-04-17
ES2729070T3 (es) 2019-10-30
CN105874109A (zh) 2016-08-17

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